EP0938151A2 - Lithium Sekundärbatterie und flüssiger Elektrolyt dafür - Google Patents

Lithium Sekundärbatterie und flüssiger Elektrolyt dafür Download PDF

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EP0938151A2
EP0938151A2 EP99102731A EP99102731A EP0938151A2 EP 0938151 A2 EP0938151 A2 EP 0938151A2 EP 99102731 A EP99102731 A EP 99102731A EP 99102731 A EP99102731 A EP 99102731A EP 0938151 A2 EP0938151 A2 EP 0938151A2
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lithium
solvent
liquid electrolyte
carbonate
lithium secondary
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French (fr)
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EP0938151A3 (de
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Juichi Arai
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Hitachi Ltd
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Hitachi Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H01M2200/10—Temperature sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a lithium secondary battery using a non-aqueous liquid electrolyte containing lithium ions as migrating ions, the liquid electrolyte for the battery and use of the battery.
  • a lithium secondary battery using a non-aqueous liquid electrolyte has high potential and energy density and distinguished storage capacity and low temperature workability and has been widely used in consumer-oriented portable electrical products. Intensive researches and developments are now underway for battery scale-up for application to power storage systems during night hours for electric cars or domestic use.
  • JP-A-7-192762 discloses mixing of a cyclic carbonate ester with flame retardant effect-expectable halogenated formate ester, thereby reducing the flammability.
  • JP-A-8-45544 discloses mixing with a halogenated ester.
  • the halogenated formate ester or halogenated ester has a lower flash point in some cases than non-halogenated cyclic carbonates and thus it seems that no satisfactory flame retardant effect can been attained thereby.
  • JP-A-4-184370 and JP-A-8-88023 disclose another approach by adding a self-extinguishing effect-expectable phosphate ester to a liquid electrolyte, but the cycle characteristics are somewhat deteriorated thereby.
  • JP-A-9-293533 discloses addition of 0.5 to 30% by weight of a fluorinated alkane to a solvent, thereby making the solvent flame-retardant, where the fluorinated alkane acts as an extinguishing agent due to the suppressing effect of these low boiling point fluorine compounds on the flammability the resulting gas mixture.
  • JP-A-9-293533 discloses a flame retardation method comprising adding a fluorine compound having a boiling point of not more than 25°C to the battery, allowing the fluorine compound to evaporate faster than the flammable solvent when the battery is exposed to high temperatures, so that the flammability of flammable solvent can be suppressed by the resulting vapors, where the non-flammable solvent is used not in the liquid electrolyte, but as separated from the liquid electrolyte.
  • An object of the present invention is to provide a lithium secondary battery free from such hazards as explosion, ignition, smoke emission, etc. due to elevated temperatures, heating, overcharging, internal short circuits, etc., a non-aqueous liquid electrolyte for the battery, and use of the battery.
  • the present invention provides a lithium secondary battery, which comprises a negative electrode, a positive electrode, a separator and a non-aqueous liquid electrolyte, the non-aqueous liquid electrolyte having an electrical conductivity of 0.05 ms/cm or more and no such a flash point as specified by JIS-K2265 flash point test.
  • the present invention provides a non-aqueous liquid electrolyte for a lithium secondary battery, which comprises an ion nonconductive solvent and a lithium ion conductive solvent and has an electrical conductivity of 0.05 mS/cm or more and no such a flash point as specified by JIS-K2265 flash point test.
  • non-flammable liquids typically non-flammable solvents are characterized in that generally the dipole moment is small and the dielectric constant is low, resulting in much poor solubility of lithium salts. Its compatibity with non-aqueous solvents having a large dipole moment and a good lithium salt dissociation capability is also low, and thus the non-flammable solvent cannot be mixed with the non-aqueous solvent, resulting in separation into two layers.
  • the non-flammable solvents fail to show all the physical properties required for the liquid electrolyte.
  • it is indispensable for scaling-up of the lithium secondary battery and widespread proliferation thereof to electric cars and domestic uses to solve the problem of liquid electrolyte flammability, i.e., the sole drawback of the lithium secondary battery.
  • the object of the present lithium secondary battery is to solve such a problem.
  • the present lithium secondary battery is characterized by comprising a non-aqueous liquid electrolyte having an electric conductivity of 0.05 mS/cm or more and no such a flash point as specified by the JIS-K2265 flash point test.
  • the present lithium secondary battery is characterized by comprising a lithium-storable and releasable negative electrode, a lithium-storable and releasable positive electrode, a separator and a lithium salt-containing non-aqueous liquid electrolyte, the non-aqueous liquid electrolyte comprising a mixed solution of an ion nonconductive solvent, preferably a non-flammable solvent having a very high flame retardancy, and a lithium ion conductive solvent, the non-aqueous liquid electrolyte having no such a flash point as specified by JIS-K2265 flash point test.
  • the non-aqueous liquid electrolyte can be made to have no such a flash point as specified by JIS-K2265 flash point test by making a ratio of the ion nonconductive solvent to the lithium ion conductive solvent to be 95-60% by volume: 5-40% by volume.
  • the present lithium secondary battery is characterized in that the non-aqueous liquid electrolyte contains at least 10% by volume of the ion nonconductive solvent and the lithium ion conductive solvent in total.
  • the present lithium secondary battery is characterized in that the non-aqueous liquid electrolyte comprises a mixed solution of an ion nonconductive solvent and a lithium ion conductive solvent and has an electrical conductivity of 01 to 3 mS/cm.
  • the present lithium secondary battery is characterized in that the non-aqueous liquid electrolyte comprises a mixed solution of an ion nonconductive solvent and a lithium ion conductive solvent and the lithium ion conductive solvent has a dipole moment of not more than 3 debyes.
  • the present lithium secondary battery is characterized in that the non-aqueous liquid electrolyte comprises a mixed solution of an ion nonconductive solvent and a lithium ion conductive solvent and the lithium ion conductive solvent comprises a solvent having a dipole moment of less than 3 debyes and a solvent having a dipole moment of not less than 3 debyes.
  • the present lithium secondary battery is characterized in that the non-aqueous liquid electrolyte comprises an ion nonconductive solvent and a lithium ion conductive solvent, and further contains an organic lithium salt and an inorganic lithium salt as lithium salts.
  • a non-aqueous liquid electrolyte for the present lithium secondary battery comprises an ion nonconductive solvent and a lithium ion conductive solvent and has an electrical conductivity of 0.1 mS/cm or more and no such a flash point as specified by JIS-K2265 flash point test.
  • non-flammable solvent the ion nonconductive solvent according to the present invention.
  • the non-flammable solvent fails to dissolve a lithium salt, but can be mixed in a compatible or dispersed state, up to a limit value corresponding to the physical properties of the non-flammable solvent, with an ion conductive solution, which comprises a non-aqueous solvent having a low dipole moment and a dissolved and dissociated lithium salt.
  • an ion conductive solution which comprises a non-aqueous solvent having a low dipole moment and a dissolved and dissociated lithium salt.
  • the present inventors have found that the resulting mixed solution can act as a liquid electrolyte.
  • liquid electrolyte according to the present invention will be hereinafter referred to as "an non-flammable liquid electrolyte”.
  • the present non-flammable liquid electrolyte is a solution comprising an ion nonconductive solvent such as a fluorinated solvent and a dissolved and dissociated lithium salt-containing non-aqueous solvent having a dipole moment of not more than 3 debyes in a compatible or dispersed state in the ion nonconductive solvent.
  • a lithium secondary battery having a very high safety can be provided by using the present non-flammable liquid electrolyte.
  • fluorinated solvent for use in the present invention includes a fluorinated ether represented by the following general formula (1): C m F 2m+1 ⁇ O ⁇ C n H 2n+1 where m is an integer of 2 to 8, n is an integer of 1 to 5; and m and n is in such a relation as m ⁇ ((6n+1)/4) .
  • These ion nonconductive solvents have a dipole moment of about 2 debyes as obtained by molecular orbital calculation.
  • the non-aqueous solvent to be mixed with the ion nonconductive solvent from the viewpoint of increasing the compatibility also has a dipole moment of desirably about 2 debyes or less, but suitably up to 3 debyes at most.
  • non-flammable fluorinated solvent the fluorinated solvent
  • the non-flammable fluorinated solvent for use in the present invention is at least one of solvents selected from perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluoropentyl methyl ether, perfluoropentyl ethyl ether, perfluoroheptyl methyl ether, perfluoroheptyl ethyl ether, etc., where the first two are particularly preferable.
  • the non-aqueous solvent for use in the present invention is at least one of non-aqueous solvents selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, etc., and fluorinated oligomers represented by the following general formula (2): where p is an integer of 2
  • At least one of organic lithium salts such as LiCF 3 SO 2 , LiN(CF 3 SO 2 ) 2 , LiN(CF 2 SO 2 ) (CF 3 CF 2 CF 2 SO 2 ), LiN(CF 3 CF 2 SO 2 ) 2 , LiC(CF 3 SO 2 ) 2 , LiC(CF 3 CF 2 SO 2 ) 2 , Li[PF 4 (CF(CF 3 ) 2 ] can be used, and at least one of inorganic lithium salts such as LiPF 6 , LiBF 4 , LiF, LiBr, LiI, LiCl, LiBr, LiClO 4 , etc. can be used.
  • organic lithium salts such as LiCF 3 SO 2 , LiN(CF 3 SO 2 ) 2 , LiN(CF 2 SO 2 ) (CF 3 CF 2 CF 2 SO 2 ), LiN(CF 3 CF 2 SO 2 ) 2 , LiC(CF 3 SO 2 ) 2 , LiC(CF 3 CF 2 SO 2 ) 2
  • Lithium salt when dissolved into the mixed solution of the non-flammable solvent and the ion conductive, non-aqueous solvent, is dissolved and dissociated by the ion conductive non-aqueous solvent, so that the resulting lithium ions and the counter anions are surround by the solvating ion conductive non-aqueous solvent, resulting in a compatible state in the non-flammable fluorinated solvent.
  • the ion conductive non-aqueous solvent With increasing lithium salt concentration, the ion conductive non-aqueous solvent will be incapable of forming a satisfactory solution zone with lithium ions or counter anions, resulting in contacts of lithium ions or counter anions with the non-flammable solvent, thereby making the energy of the solvent system so unstable that, a larger solvation zone may result through gathering of several solvations, and the non-flammable solvent molecules may form a state free of ion direct contact.
  • the ion-containing non-aqueous solvent molecules form a micelle-like state in the fluorinated solvent, i.e. a dispersion state of the ion conductive solvent in the ion nonconductive solvent (non-flammable solvent).
  • a mixed solution containing the non-flammable solvent molecules and the lithium salt-dissolved and dissociated non-aqueous solvent molecules in a compatible or dispersed state is utilized as a non-flammable liquid electrolyte.
  • the lithium salt concentration exceeds a limit value depending on the compatibility of the non-flammable molecules and the non-aqueous solvent molecules, solubilities of lithium salts in non-aqueous solvent, etc.
  • the solution of the non-aqueous solvent containing the lithium salt as dissolved therein will be separated from the non-flammable solvent in the mixed, solution and the mixed solution will no more work as the liquid electrolyte.
  • the non-flammable solvent such fluorinated solvents as perfluorobutyl methyl ether and perfluorobutyl ethyl ether are preferable.
  • non-graphitizing carbon natural or artificial graphite carbon, or tin oxide, silicon or germanium compound, or lithium metal or lithium alloy or the like can be used as an appropriate negative electrode active substance.
  • lithium composite oxides with a transition metal such as cobalt, nickel, manganese, etc., or the lithium composite oxides, part of whose lithium sites or transition metal sites is replaced with cobalt, nickel, manganese, aluminum, boron, magnesium, iron, copper, etc. or iron complex compounds such as ferrocyan blue, berlin green, etc. can be used as an appropriate positive electrode material.
  • a microporous polymer film can be used, and include films of, for example, nylon, cellulose, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, polybutene, etc.
  • the battery is not limited to particular shapes, and can take any appropriate shape such as cylindrical shape, a coin shape, a square shape.
  • the battery is also not limited to particular capacities, and can have any appropriate capacity of 5 to 6 Wh for the domestic use to 500 to 600 Wh for the domestic power storage or electric cars.
  • liquid electrolyte which comprises:
  • the fluorinated solvent (a) for use in the present invention includes methyl perfluoroalkyl ethers represented by the following general formula (1'): C n F 2n+1 ⁇ O ⁇ CH 3 where n is an integer of 4 to 12.
  • the low dipole moment solvent (b) having a dipole moment of less than 3 debyes at least one of such linear solvents as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), methyl trifluoroethyl carbonate (MTFEC), diglyme (DGM), dimethoxyethane (DME) and triglyme (TGM) can be used.
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • MPC methyl propyl carbonate
  • MTFEC methyl trifluoroethyl carbonate
  • DGM diglyme
  • DME dimethoxyethane
  • TGM triglyme
  • a high dipole moment solvent having a dipole moment of not less than 3 at least one of such solvents as ethylene carbonate (EC), propylene carbonate (PC), trifluoropropylene carbonate (TFPC), chloroethylene carbonate (CIEC), vinylene carbonate (VC), butylene carbonate (BC), dimethylvinylene carbonate (DMVC) and ⁇ -butyrolactone (GBL) can be used.
  • EC ethylene carbonate
  • PC propylene carbonate
  • TFPC trifluoropropylene carbonate
  • VC vinylene carbonate
  • BC butylene carbonate
  • DMVC dimethylvinylene carbonate
  • GBL ⁇ -butyrolactone
  • organic lithium salt those mentioned before can be used.
  • inorganic lithium salt those mentioned before can be also used.
  • a lithium secondary battery using a non-flammable liquid electrolyte comprising not less than 80% by weight of methyl perfluorobutyl ether as a fluorinated solvent, less than 20% by volume of at least one of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate as a low dipole moment solvent and 0.1 to 10% by volume of at least one of the above-mentioned compounds as a high dipole moment solvent, and further containing 0.2 to 1.2 moles/l of LiN(SO 2 CF 2 CF 3 ) 2 as an organic lithium salt and 0.005 to 0.5 moles/l of LiPF 6 as an inorganic lithium salt, preferably the liquid electrolyte having no such a flash point as specified by JIS-K2265 flash point test, is preferably provided.
  • the fluorinated solvent for use in a liquid electrolyte is a non-flammable solvent without a flash point, and compatible with a low dipole moment solvent or a high dipole moment solvent.
  • the fluorinated solvent does not require the particular requires lithium salt solubility that is necessary for the ordinary solvent for use in the liquid electrolyte.
  • various linear fluorinated solvents can be used as non-flammable solvents.
  • Perfluoroalkanes, semifluoroalkanes, their chlorine- or bromine-introduced derivatives, etc. can be also used, though these are not preferable substances when their environmental influence or toxicity is taken into consideration.
  • Hydrofluroethers used as a substitute for flon cleaning agents from the viewpoint of environmental protection have no such problems and are not expensive, as compared with the ordinary solvents for use in the liquid electrolyte, and are rather suitable as a non-flammable solvent for use in the non-flammable liquid electrolyte.
  • methyl perfluoroalkyl ethers represented by the following general formula (1') are preferable fluorinated solvents for use in the present invention: C n F 2n+1 ⁇ O ⁇ CH 3 where n is an integer of 4 to 12, and include, for example, methyl perfluorobutyl ether, methyl perfluoropentyl ether, methyl perfluorohexyl ether, methyl perfluorobutyl ether, methyl perfluorooctyl ether, methyl perfluorononyl ether, methyl perfluorodecyl ether, methyl perfluoroundecyl ether, methyl perfluorododecyl ether, etc.
  • the fluorinated solvent has a low dipole moment.
  • the linear low dipole moment solvent as mentioned before has a better compatibility.
  • a mixed solution of the hydrofluoroether and the low dipole moment solvent can dissolve the organic lithium salt up to about 1.2 M even at a concentration of not less than 80% by volume of the fluorinated solvent, though depending on the species and mixing proportion of mixed solution.
  • the soluble organic lithium salts are those mentioned before. Above all, LiN(SO 2 CF 2 CF 3 ) 2 , LiC(SO 2 CF 2 CF 3 ) 3 , LiC(SO 2 CF 3 ) 3 and Li[PF 4 (CF(CF 3 ) 2 ] having a low reactivity with aluminum at high potentials in the current batteries using aluminum as a positive electrode current collector are preferable.
  • a non-flammable liquid electrolyte can be provided by using the foregoing materials as components, but to improve the load characteristics, it is further necessary to provide a film capable of reducing the lithium ion incoming or outgoing resistance through the boundary surface of active substance when charged or discharged, as called SEI (surface electrode interface) (see, for example, J. Electrochemical Soc., P2882, vol. 142 (1995), etc.).
  • SEI surface electrode interface
  • Properties of reaction products in the solvent near the electrode depend on the species of highly reactive compounds present in the liquid electrolyte, the species and mixing proportion of solvents to be mixed to serve as the reaction field for these compounds, etc. It seems that no satisfactory SEI for maintaining the load characteristics can be obtained in the liquid electrolyte comprising the foregoing component materials.
  • a high dipole moment solvent having a high coordinatability with lithium ions is further mixed as a precursor for SEI in the present invention.
  • the liquid electrolyte With increasing amount of the high dipole moment solvent, the liquid electrolyte will be no more applicable, because of occurrence of phase separation. Thus, it is preferable to add 0.1 to 10% by volume of the high dipole moment solvent thereto.
  • the load characteristics of the liquid electrolyte can be much more stabilized by adding an inorganic lithium salt having a very low solubility, per se, in the fluorinated solvent or the mixed solution of the fluorinated solvent.
  • the inorganic lithium salt to be added thereto is those mentioned before.
  • fluorine-containing compounds capable of forming an electrochemically stable film on the aluminum surface such as LiPF 6 , LiBF 4 and LiF are preferable. It is preferable to add 0.005 to 0.5 moles/l of the inorganic lithium salt thereto, due to their low solubility.
  • the present invention also provides an electrical appliance using the present lithium secondary batteries, characterized by comprising a means for protecting overcharging and overdischarging of the lithium secondary batteries, the means being free from temperature and pressure detection of the lithium secondary batteries, a means for detecting the voltage or current of the lithium secondary batteries, and a means for on-off controlling the power source on the basis of detected voltage or current values.
  • Tridecafluorobutyl methyl ether HFE 7100 (trademark of a product commercially available from Sumitomo-3M Co., Japan; dipole moment obtained by molecular orbital calculation (MOPAC) : 2.37 debyes) as a non-flammable fluorinated solvent, ethyl methyl carbonate (dipole moment likewise obtained : 0.887 debyes) as a non-aqueous solvent and lithium bistrifluoromethyl sulfonyl imide (LiTFMSI) as a lithium salt were used to evaluate relations between lithium salt concentration and ionic conductivity, and also solubility and miscibility of the liquid electrolytes of Examples 1 to 9 and that of Comparative Example 1 in solvent mixing proportions as shown in the following Table 1.
  • Non-flammable solvent HFE7100 Mixing proportion (vol. %)
  • Non-aqueous solvent EMC Mixing proportion (vol. %)
  • Example 1 85 15
  • Example 2 80 20
  • Example 3 70 30
  • Example 4 60
  • Example 5 50
  • Example 6 40
  • Example 7 30
  • Example 8 20
  • Example 9 10 90 Comp. Ex. 1 0 100
  • Fig. 1 is a graph showing relations between lithium salt concentration and changes in ionic conductivity.
  • the ionic conductivity increases with increasing EMC mixing proportion, and above 50 vol. % of EMC mixing proportion the ionic conductivity no more decreases even at a lithium salt concentration over 1 M (mole/liter), showing that LiTFSI can be much more dissolved.
  • dispersion or separation of the non-aqueous solvent in or from the fluorinated solvent is not observable in the evaluated lithium salt concentration range.
  • Non-aqueous solvent Dipole moment of non-aqueous solvent Solvent compatibility State of liquid electrolyte Ionic conductivity (mS/cm) LiTFSI concentration (M)
  • Example 10 DMC 0.759 Compatible Compatible 0.84 1
  • Example 11 DEC 0.967 Compatible Compatible 0.68 0.8
  • Example 12 TFEMC 2.231 Compatible Compatible 0.25 0.6
  • Example 13 BTFPC 2.719 Compatible Compatible 0.15 0.3
  • Example 14 DOL 1.256 Compatible Separated 0.05 0.2 Comp. Ex. 2 PC 4.811 Separated Separated Unmeasurable Unpreparable Comp. Ex. 3 EC 4.616 Separated Separated Unmeasurable Unpreparable Comp. Ex. 4 GBL 4.228 Separated Separated Unmeasurable Unpreparable Comp. Ex. 5 BC 5.009 Separated Separated Unmeasurable Unpreparable
  • solvents having a higher dipole moment than 3 debyes of Comparative Examples 2 to 5, i.e. PC, EC, GBL and BC are not compatible with the non-flammable solvent HFE7100. It seems therefrom that the compatibility largely depends on differences in the solvent polarity. It is also noted that a solvent of cyclic molecules, even if the dipole moment is lower than 3 debyes, for example, DOL (1.256 debyes), takes a dispersed state, when mixed with the non-flammable solvent. Even solvents of linear molecules have a decreasing lithium salt solubility with increasing dipole moment such as BTEPC (2.719 debyes). It can be seen from the foregoing that the solvent to be mixed with the non-flammable fluorinated solvent preferably have a dipole moment of not more than 3 debyes.
  • Fig. 2 is a graph showing relations between lithium salt concentrations in relation to solubility dependency of various lithium salts in a mixed solution of 80 vol. % HFE7100 and 20 vol. % MEC and ionic conductivity of the resulting liquid electrolytes.
  • lithium bispentafluoroethyl sulfonyl imide LiBETI
  • LiFBMSI lithium perfluorobutylmethylsulfonyl imide
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • organic lithium salts having a fluoro chain such as LiTFSI, LiBETI, LiFBMSI, etc. have higher solubility and dissociability and also a better electrical conductivity in the mixed solution than inorganic lithium salts such as LiPF 6 , LiBF 4 , etc., because it seems that the anions dissociated from the inorganic lithium salt have a higher orientativeness and substantially zero dipole moment (e.g. 0.001 debye with PF 6 - and 0.001 debye with BF 4 - as calculated), and also have so small a molecular radius that their affinities toward the non-flammable fluorinated solvent having a high electrificability and a low dielectric constant are lowered.
  • inorganic lithium salts such as LiPF 6 , LiBF 4 , etc.
  • anions dissociated from the organic lithium salts have a significant dipole moment (1.23 debyes with TFSI - , 1.103 debyes with BETI - ,and 8.468 debyes with FBMSI - as calculated) and a larger molecular radius.
  • the organic anions shown herein have a fluoro chain and a good affinity toward the non-flammable fluorinated solvent, contributing to the higher solubility. That is, organic lithium salts are more preferable electrolyte materials for the non-flammable liquid electrolyte. Above all, LiTFSI having a shorter fluoro chain has a better counter anion diffusibility and is a distinguished electrolyte material for the non-flammable liquid electrolyte.
  • Lithium secondary batteries of Examples 19 to 23 using non-flammable liquid electrolytes of various compositions shown in the following Table 3 and a lithium secondary battery of Comparative Example 6 using the conventional liquid electrolytes shown in the same Table 3 were prepared to evaluate battery characteristics and safety.
  • the results are also shown in Table 3, where HFE7200 is tridecafluorobutyl ethyl ether, a product commercially available from Sumitomo-3M Co., Japan. Solvent mixing proportion (vol.
  • Fig. 3 is a vertical cross-sectional view of a cylindrical battery, 18 mm in outer shell diameter and 65 mm high, as used in these Examples and Comparative Example, where artificial graphite was used for negative electrode active substance 9, lithium cobaltate for positive electrode active substance 10, and 25 ⁇ m-thick microporous polyethylene film for separator 11.
  • the battery was prepared by introducing the liquid electrolyte therein by vacuum impregnation in a glove box, then providing thereon battery positive electrode cover 13 with two internal pressure release valves, whose pressure limit was 5 atmospheres, and tightly sealing the cover to battery can 14 by laser welding (welding seam: 15).
  • a slurry of positive electrode mixture was prepared by adding 7 parts by weight of acetylene black as a conductor and 5 parts by weight of polyvinylidene fluoride (PVDF) as a binder to 100 parts by weight LiCoO 2 as a positive electrode active substance, and further adding N-methyl-2-pyrrolidone thereto, followed by mixing.
  • PVDF polyvinylidene fluoride
  • a slurry of negative electrode mixture was likewise prepared by adding 10 parts by weight of PVDF as a binder to 100 parts by weight graphite powder, 8 ⁇ m in average particle size, comprising 1 to 20 wt. % of rhombohedral crystal, the balance being hexagonal crystal as a negative electrode active substance and further adding N-methyl-2-pyrrolidone, followed by mixing.
  • the positive electrode mixture was applied to both sides of a 20 ⁇ m-thick aluminum foil and vacuum dried at 120°C for one hour. After the vacuum drying, a positive electrode having a thickness of 195 ⁇ m was press molded therefrom by a roller press. The amount of the applied mixture per unit area was 55 mg/cm 2 .
  • the negative electrode mixture was applied to both sides of a 10 ⁇ m-thick copper foil and vacuum dried at 120°C for one hour. After the vacuum drying, a negative electrode having a thickness of 175 ⁇ m was press molded by a roller press. The amount of the applied mixture per unit area was 25 mg/cm 2 . Proportion of rhombohedric crystal in the graphite powders can be adjusted by heat treatment at 900°C or higher, and a smaller proportion thereof is preferable.
  • JIS SUS 304 or 316 austenite stainless steel was used for battery can 14 and battery positive electrode cover 13.
  • the batteries of Examples 19 to 23, using the present non-flammable liquid electrolyte are characteristically comparable with the battery of Comparative Example 6 using the conventional liquid electrolyte (initial capacities of 1,200 mAh or higher and capacity maintenance rate of 90% or higher), and have a much improved safety because of being quite free from any risk of ignition.
  • Negative electrode 9, positive electrode 10, battery can 14 and battery positive electrode cover of the battery were made from the same materials as used in Examples 19 to 23.
  • the battery positive electrode cover 13 was provided with an internal pressure release valve 12, whose pressure limit was 5 atmospheres, and was tightly sealed to battery can 14 by laser welding (welding seam: 15).
  • the present non-aqueous, non-flammable liquid electrolyte has good battery characteristics such as battery capacity and load characteristics, even though its ionic conductivity is low, as compared with the conventional non-aqueous liquid electrolyte.
  • the ion migration route formed by the ion conductive, non-aqueous solvent mixed with the non-flammable fluorinated solvent is not interfered.
  • the non-flammable solvent acts likewise, i.e. like a so-called liquid separator.
  • the ion concentration in the ion migration route is higher than in the conventional non-aqueous liquid electrolyte and thus a liquid electrolyte system of much higher efficiency has been established in the present invention than the conventional system.
  • Fig. 5 is a graph showing relations between the contents of various ion conductive solvents mentioned before and the flash point according to JIS-K2265 flash point test, where the non-flammable solvent was HFE7100. As shown in Fig. 5, the contents showing no such a flash point as specified by JIS-K2265 flash point test depended on the species of solvents, where B.P. stands for boiling point. Less than 30% by volume of EMC and DMC and less than 20% by volume of DME are preferable. Not more than 30% by volume of TGM and DEC are preferable.
  • Fig. 6 is a partially cutaway view showing a cylindrical lithium secondary battery, 18 mm in diameter and 65 mm high, using the present non-aqueous liquid electrolyte.
  • a paste of negative electrode mixture was prepared by dissolving and kneading 90 parts by weight of graphite carbon materials as a negative electrode active substance into N-methyl-pyrrolidone together with 10 parts by weight of polyvinylidene fluoride (PVDF) as a binder.
  • the paste of negative electrode mixture was applied to both sides of a 10 ⁇ m-thick copper foil current collector 1, dried by heating and press heated to make negative electrode 2. Then, negative electrode tab terminal 3 was fixed to one end of the electrode by welding a nickel foil thereto.
  • a paste of positive electrode mixture was prepared by dissolving and kneading 80 parts by weight of LiCoO 2 as a positive active substance, 8 parts by weight of acetylene black as a conducting promoter, 7 parts by weight of PVDF into N-methylpyrrolidone.
  • the paste of positive electrode mixture was applied to both sides of a 20 ⁇ m-thick aluminum foil current collector 4, dried by heating and press heating to make positive electrode 5.
  • Positive electrode tab terminal 6 was fixed to one end of the electrode by welding a nickel foil thereto.
  • Porous polypropylene separator 7 was sandwiched between these electrodes, followed by winding, thereby forming an electrode laminate. Then, the electrode laminate was inserted into battery can 19, while sandwiching negative electrode insulator 8 between the electrode laminate and the can bottom, and negative electrode tab terminal 3 was welded to the can bottom. Positive electrode tab terminal 6 was welded to positive electrode cover 20 through positive electrode insulator 21.
  • liquid electrolyte A 83 vol. % of methyl perfluorobutyl ether as a fluorinated solvent and 15 vol. % of EMC were mixed together, and further 0.8 moles/l of LiN(SO 2 CF 2 CF 3 ) 2 as a lithium salt was added thereto. Then, 2 vol. % of EC was dissolved into the resulting solution, and further 0.1 mole/l of LiPF 6 as an inorganic lithium salt was dissolved therein to prepare liquid electrolyte A. It was found by JIS-K2265 Cleveland open-cup flash point test that the liquid electrolyte A had no such a flash point as specified in the JIS-K2265 flash point test.
  • liquid electrolyte A was introduced into the battery made ready as above by vacuum impregnation, and then positive electrode cover 20 and battery can 19 were tightly sealed together by caulking to prepare a battery A.
  • a lithium secondary battery R1 was prepared, using a solvent solution comprising 34 vol. % of EC and 66 vol. % of DMC and further containing 1.0 M LiPF 6 as dissolved therein as a liquid electrolyte R1. It was found by the JIS-K2265 flash point test that the liquid electrolyte R1 had a flash point of about 35°C.
  • a liquid electrolyte B was prepared by mixing 85 vol. % of methyl perfluorobutyl ether as a fluorinated solvent with 15 vol. % of EMC, followed by dissolving 0.8 moles/l of LiN(SO 2 CF 2 CF 3 ) 2 as a lithium salt therein.
  • the liquid electrolyte B was introduced into the same battery as in Example 30 to prepare a lithium secondary battery R2.
  • the liquid electrolyte B had the same composition as that of liquid electrolyte A except that neither EC nor LiPF 6 were contained therein. It was found by the JIS-K2265 flash point test that the liquid electrolyte B had no such a flash point as specified therein.
  • Load characteristics of the batteries prepared in the foregoing manner were evaluated on the basis of 140 mA as 0.1C (10-hour rate) by increasing a current from 140 mA up to 1,400 mA (1C) successively at a rate of 140 mA.
  • Charging conditions were constant-current and constant-voltage (CC-CV) conditions by increasing the current of constant-current from 140 mA up to 1,400 mA successively at a rate of 140 mA as mentioned above, and the voltage for constant-voltage charging was set to 4.1 V with the end point being set to 15 hours or not more than 10 mA. Results of the test are shown in Fig. 7.
  • the discharge capacity of battery R2 using the non-flammable liquid electrolyte B is considerably lowered at the current of 0.3C (420 mA) or more.
  • the present battery A using the non-flammable liquid electrolyte A containing both EC and LiPF 6 has a drastically higher discharge capacity than that of battery R2, though a little inferior to that of battery R1.
  • the drastically higher discharge capacity is surprising, when the ionic conductivities of these liquid electrolytes are taken into consideration.
  • Disk electrodes 15 mm in diameter, were coated with the same positive electrode material and negative electrode materials as used in Example 30, on their one side, respectively, to make disk positive electrode 23 and disk negative electrode 22, and thus coated disk electrodes were made into a test battery as shown in Fig. 9, using a disk separator 24, 18 mm in diameter, to evaluate battery characteristics.
  • numeral 25 is a negative electrode terminal, 26 a positive electrode terminal and 27 a Teflon fastening screw.
  • a test battery C1 was prepared, using a liquid electrolyte C prepared by adding 0.05 g/l at PC (propylene carbonate) to liquid electrolyte B. That is, the liquid electrolyte C comprised 83 vol. % of methyl perfluorobutyl ether, 15 vol. % of EMC and 2 vol. % of PC.
  • a test battery C2 was prepared, using a liquid electrolyte D prepared by replacing PC with the same amount of BC (butylene carbonate) in the liquid electrolyte C. That is, the liquid electrolyte D comprised 83 vol. % of methyl perfluorobutyl ether, 15 vol. % of EMC and 2 vol. % of BC.
  • a test battery C4 was prepared, using a liquid electrolyte F prepared by replacing PC with the same amount of TFPC (trifluoromethylpropylene carbonate) in the liquid electrolyte C. That is, the liquid electrolyte F comprised 83 vol. % of methyl perfluorobutyl ether, 15 vol. % of EMC and 2 vol. % of TFPC.
  • test battery RC1 was prepared, using the liquid electrolyte B.
  • Discharge capacities of the batteries so prepared were compared by charging at a constant-current and constant-voltage (4.1 V) with the end point set to 5 ⁇ A by increasing a current value from 0.05 mA up to 5 mA successively at a rate of 0.05 mA and by discharging a constant current.
  • the results are shown in Fig. 10.
  • test battery C6 was prepared, using the liquid electrolyte A.
  • a test battery C7 was prepared, using a liquid electrolyte H obtained by changing the amount of LiPF 6 to 0.005 moles/l in the liquid electrolyte A.
  • a test battery C8 was prepared, using a liquid electrolyte I obtained by changing the amount of LiPF 6 to 0.2 moles/l in the liquid electrolyte A.
  • a test battery CR2 was prepared, using a liquid electrolyte J obtained by changing the amount of LiPF 6 to 0 mole/l in the liquid electrolyte A.
  • the load characteristics can be further improved by further adding an inorganic lithium salt LiPF 6 to the high dipole moment solvent.
  • the amount of the inorganic lithium salt LiPF 6 has an optimum value, and the optimum limit is 0.1 mole/l in case of the liquid electrolyte A system.
  • Battery A of Example 30 and battery R1 of Comparative Example 9 were subjected to safety tests such as (1) nail driving test and (2) overcharging test.
  • Nail driving test was carried out under the following four conditions: (1-1) room temperature at 30 mm/sec, (1-2) room temperature at 5 mm/sec, (1-2) room temperature at 1 mm/sec, and (1-4) 60°C at 1 mm/sec. The results are shown in the following Table 5. Test conditions Battery A Battery R1 (1-1) 3/3 Normal 3/3 Normal (1-2) 3/3 Normal 1/3 Ignited (1-3) 3/3 Normal 2/3 Ignited (1-4) 3/3 Normal 3/3 Ignited
  • the present non-flammable liquid electrolyte had an equivalent or superior safety to that of the conventional liquid electrolyte in the overcharging test in spite of such a fear that dendrite short circuits would be liable to take place due to the low ionic conductivity and the present non-flammable liquid electrolyte would be inferior to that of the conventional liquid electrolyte having a high ionic conductivity.
  • Vapor liquid phase diagrams were prepared at the time of mixing a non-flammable solvent and a non-aqueous solvent.
  • Fig. 12 is a vapor liquid phase diagram of a mixed solvent of a non-flammable solvent HFE 7100 and a non-aqueous solvent EMC.
  • this mixed solvent there is no flash point until 20% by volume of EMC in the mixture as shown previously.
  • the vapor of the mixed solvent contains 93% by volume or more of non-flammable solvent HFE 7100 as shown in Fig. 12, resulting in making the flammability of the vapor remarkably low.
  • Fig. 13 is a vapor liquid phase diagram of a mixed solvent of HFE 7100 and DMC.
  • a difference in boiling points ⁇ T(B.P.) is 30°C (the boiling point of DMC is 90°C and the boiling point of HFE is 60°C) and ⁇ T(B.P.) of HFE 7100-EMC system is narrower than about 50°C, the vapor phase volume percentage of HFE 7100 in the region of lower mixing ratio of DMC becomes lower.
  • the area having no flash point in the HFE 7100-DMC system becomes narrower than that in the HFE 7100-EMC system.
  • Fig. 14 is a vapor liquid phase diagram of a mixed solvent of HFE 7200 and EMC.
  • ⁇ T B.P.
  • HFE 7200 has a F/H ratio in the molecule of 1.8, which value is lower than the F/H ratio of 3 of HFE 7100, the fire extinguishing function is low, resulting in making this system flammable even in a low mixing ratio of EMC of 20% by volume.
  • Solvent composition 48 HFE 7100 + DME + PC 49 HFE 7100 + DME + CLEC 50 HFE 7100 + DME + DMVC 51 HFE 7100 + DME + EC 52 HFE 7100 + DME + BC 53 HFE 7100 + DME + TFPC
  • the lithium salt was dissolved upto 0.6 M, but the conductivity showed a maximum value of 0.55 mS/cm at 0.4 M.
  • the conductivity increased with a mixing ratio of DMC.
  • the conductivity showed 1.15 mS/cm at a shifted maximum value of 0.8 M.
  • Electrolytes were prepred by mixing HFE 7100 with the following two kinds of non-aqueous solvents to examine the lithium salt concentration dependency. EMC 15% by volume + DME 5% by volume EMC 10% by volume + DME 10% by volume
  • the maximum value was 0.72 mS/cm at the lithium salt concentration of 0.6 M. In the case of the mixture of DOL and DME, the maximum value was 0.68 mS/cm at the lithium salt concentration of 0.8 M.
  • the lithium salt was dissolved in an amount of upto 0.2 M in a two component mixing system containing 20 or 30% by volume. Even if 40% by volume of DGM was contained, the dissolution limit was 0.4 M.
  • the conductivity was as high as 2.7 mS/cm.
  • Fig. 21 The results are shown in Fig. 21.
  • a non-aqueous solvent such as DMC and DME, it is possible to obtain a lithium salt dissolving ability of 1 M or more even at a low mixing ratio of DGM of 10% by volume.
  • HFE 7100 80 : 20
  • HFE 7100 70 : 30
  • HFE 7100 : TGM 60 : 40
  • HFE 7100 : TGM : DME 80 : 15 : 5
  • HFE 7100 : TGM : DME 80 : 10 : 10
  • Fig. 24 shows discharge curves at a second time of these batteries of Examples 82 and 83.
  • FIG. 25 shows the test results of charge-discharge cycle of this battery. As shown in Fig. 25, the capacity lowering rate after 50 cycles is within 20% of the maximum initial capacity.
  • Fig. 26 shows a system structure for driving an electric car using lithium secondary batteries given in
  • the key switch is turned on and the accelerator is stepped on. Motor torque or revolution can be controlled according to step angles of the accelerator.
  • the accelerator is stepped off, the regenerative brake corresponding to the engine brake is actuated.
  • the brake is stepped on, the regenerative braking force is made to further increase.
  • Control system is based on IGBT vector control inverter system using an induction motor, and the power source voltage is set to 336 V from the viewpoint of the IGBT withstand voltage.
  • the output is set to a maximum power of 45 kW and maximum torque of 176 N ⁇ m from the viewpoint of the power performance capabilities (acceleration capability and gradability) required for the car, and the rated output is set to 30 kW from the viewpoint of the maximum speed specification.
  • Main control items are a forward- and backward-driving control, a regenerative control and also a fail-safe control.
  • Cooling water channels are provided in the aluminum frame housing the motor proper and made into an optimum shape by temperature elevation simulation. Cooling water flows into the water channels in the frame through the water inlet, flows out after absorption of heat from the motor proper and is cooled by a radiator in the recycle route.
  • the water cooling system can improve the cooling performance about 3 times as high as that of the air cooling system.
  • Inverter uses IGBT as a power device and generates heat of about several kW maximum at the maximum output. Besides, surge absorber resistances, filter condensers, etc. also generate heat, and thus it is necessary to efficiently cool these parts, thereby suppressing them below the allowable temperatures. Particularly, cooling of IGBT is a problem, and air cooling, water cooling, oil cooling, etc. can be selected as its cooling system. In this Example, a forced cooling system with easy handling and efficient cooling is selected.
  • a protection circuit for the lithium secondary batteries as the power source is provided in this Example, as shown in Fig. 26, and protects the batteries from overcharging and overdischarging.
  • the protection circuit comprises balance compensation circuits each for adjusting the cell voltage of the respective batteries as shown in Fig. 27, which are thus provided in the batteries, respectively.
  • the balance compensation circuits are controlled by a microcomputer.
  • the conventional lithium secondary batteries using a flammable liquid electrolyte have been monitored by detecting temperature or pressures by thermistors provided on the respective batteries, whereas this Example uses the non-flammable liquid electrolyte having such no flash point that a flame, even if made to approach the liquid electrolyte, will not spread to the liquid electrolyte, unnecitating any special monitoring of temperatures or pressures. That is, the safety mechanism as the protection circuit can be reduced in the present invention thereby. As shown in Fig. 26, the power source will be automatically turned on or off, when the overcharging is detected.
  • the present lithium secondary batteries can be likewise used in an electric car using a permanent magnetic type synchronous motor and a DC motor besides the induction motor, where INV is an inverter, IM an induction motor, E an encoder, SM a synchronous motor, PS a position sensor, PWM a pulse width modulation, DCM a DC motor, CH a chopper, N* a speed instruction and T* a torque instruction, and the rows under the respective captioned motor types show control system, system structure and main control parameter, respectively.
  • Fig. 29 shows a system structure for power storage during night hours, using the present lithium secondary batteries as given in Examples 1 to 84.
  • This power storage system is based on 2,000 kW x 4 h and cell capacity of 1,000 Wh, using 24 parallel connections of 360 batteries in series connections.
  • This Example is directed to a large capacity of power storage and is effective also for the domestic air conditioners, electric water-heating systems, etc.
  • the present invention can make essentially non-flammable lithium secondary batteries for domestic uses and also large capacity lithium secondary batteries for use in power storage or electric cars and can provide lithium secondary batteries having a drastically improved safety and a high reliability, applicable to various uses.
  • the present liquid electrolyte is non-flammable and thus the volemic restriction to the liquid electrolyte to be stocked at the production sites can be lessened, so that much more liquid electrolyte can be stocked for the production than at present, with contributable merits to production or inventory adjustment, etc.

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